Fuel soluble synergistic cleaning mixture for high pressure gasoline engines
阅读说明：本技术 用于高压汽油发动机的燃料可溶性协同清洁混合物 (Fuel soluble synergistic cleaning mixture for high pressure gasoline engines ) 是由 查尔斯·沙纳汉 米歇尔·纽科尔斯 于 2019-07-19 设计创作，主要内容包括：本公开涉及用于减少在高燃料压力下操作的汽油发动机中的燃料喷射器沉积物的方法和燃料组合物。所述燃料组合物包括在所述汽油范围内沸腾的烃和协同燃料喷射器清洁混合物。(The present disclosure relates to methods and fuel compositions for reducing fuel injector deposits in gasoline engines operating at high fuel pressures. The fuel composition includes a hydrocarbon boiling in the gasoline range and a synergistic fuel injector cleaning blend.)
A method of reducing fuel injector deposits in a gasoline engine , the method comprising:
providing a fuel composition into a fuel injector of a gasoline engine at a pressure of about 500 to about 7,500psi and combusting the fuel composition in the gasoline engine;
the fuel composition includes a major amount of gasoline and a minor amount of a fuel injector cleaning blend;
the fuel injector cleaning mixture includes a th additive of formula I and a second additive of formula II
Wherein
R and R' are independently an alkylene linking group having from 1 to 10 carbon atoms;
R1is a hydrocarbyl or optionally substituted hydrocarbyl or aryl or optionally substituted aryl;
R2independently a linear or branched C1 to C4 alkyl group;
R3is hydrogen or C1 to C4 alkyl;
R4is a hydrocarbyl group;
R5is hydrogen, alkyl, aryl, -OH, -NHR6Or a polyamine, and wherein R6Is hydrogen or alkyl.
2. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein the ratio of the formula I additive to the formula II additive is from about 1:8 to about 8: 1.
3. The method of reducing fuel injector deposits in a gasoline engine of claim 2, wherein the fuel composition comprises from about 1.5 to about 100ppmw of the additive of formula I and from about 3 to about 800ppmw of the additive of formula II; and/or wherein said fuel composition comprises no more than about 600ppmw of said fuel injector cleaning mixture.
4. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein the fuel composition further comprises from about 45 to about 1000ppmw of an individual Intake Valve Deposit (IVD) control additive selected from the group consisting of Mannich detergents, polyetheramine detergents, hydrocarbyl amine detergents and combinations thereof.
5. The method of reducing fuel injector deposits in a gasoline engine of claim 4 wherein the fuel composition further comprises at least additives selected from the group consisting of antioxidants, carrier fluids, metal deactivators, dyes, markers, corrosion inhibitors, biocides, antistatic additives, drag reducers, demulsifiers, emulsifiers, dehazers, anti-icing additives, anti-knock additives, anti-valve seat recession additives, lubricity additives, surfactants, and combustion improvers.
6. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein the fuel injector cleaning mixture achieves cleaning of about 30% to about 100% of fuel injector deposits in the gasoline engine when supplied at a pressure of about 1,000psi to about 7,500psi and when cleaning of the injector deposits is measured by at least of long term fuel adjustment, injector pulse width, injection duration, injector flow rate, and combinations thereof.
7. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein R and R' are independently alkylene linking groups having 1 to 3 carbon atoms, and R1Is a C8 to C20 hydrocarbyl group.
8. The method of reducing fuel injector deposits in a gasoline engine of claim 7 wherein R' comprises a methylene linking group.
9. The method of reducing fuel injector deposits in a gasoline engine as recited in claim 8, wherein R2Is methyl.
10. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein the formula II additive comprises a hydrocarbyl-substituted succinimide derived from ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N' - (iminobis-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof.
11. The method of reducing fuel injector deposits in a gasoline engine of claim 10 wherein R in the compound of formula II4Is a hydrocarbyl group having a number average molecular weight of from about 450 to about 3000, and R5Derived from tetraethylenepentamine and derivatives thereof.
12. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein the fuel composition is provided at a pressure of about 500 to about 4,000 psi.
13. The method of reducing fuel injector deposits in a gasoline engine as recited in claim 1, wherein R1Is oleyl-derived, and wherein R5Derived from ethanediAmines, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N-N' - (iminobis-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof.
14. The method of reducing fuel injector deposits in a gasoline engine of claim 1 wherein R and R' are independently alkylene linking groups having 1 to 3 carbon atoms, R1Is a C8 to C20 hydrocarbyl group, and wherein R in the compound of formula II4Is a hydrocarbyl group having a number average molecular weight of from about 450 to about 3000, and R5Derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-N' - (iminodi-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof.
15. The method of reducing fuel injector deposits in a gasoline engine of claim 14 wherein R' is a methylene linking group; and/or wherein R2Is methyl.
Technical Field
The present disclosure relates to a method for reducing fuel injector deposits in gasoline engines operating at high fuel pressures. More particularly, the present disclosure relates to a method of cleaning a fuel injector operating at high fuel pressures by combusting a gasoline composition comprising a synergistic combination of fuel-soluble cleaning mixtures.
Background
For many years, considerable work has been devoted to additives for controlling (preventing or reducing) deposit formation in the fuel intake system of gasoline internal combustion engines. In particular, additives that are effective in controlling fuel injector deposits, intake valve deposits, and combustion chamber deposits are the focus of significant research activity in the field. However, previous fuel additives are generally less efficient when used in newer engine technologies.
For example, previous carburettor engines typically operate at fuel pressures of 4 to 15psi and previous multi-port fuel injection engines are designed to operate at fuel pressures of 30 to 60 psi. in addition , newer engine technologies are being developed for non-idle operation at fuel pressures above 500 psi.
For example, fuel additives (such as hydrocarbyl-substituted succinimides, commonly used as detergents in fuels for keeping injectors clean when operating at low pressures) do not provide the same degree of injector effectiveness when operating in gasoline engines at high fuel pressures.
Disclosure of Invention
In methods or embodiments, a method of reducing fuel injector deposits in a high pressure gasoline engine is provided the method includes injecting a fuel composition into the gasoline engine at a pressure of about 500 to about 7,500psi (e.g., a non-idle pressure) and combusting the fuel composition in the gasoline engine
Wherein R and R' are independently an alkylene linking group having from 1 to 10 carbon atoms (and from 1 to 3 carbon atoms in other methods); r1Is a hydrocarbyl or optionally substituted hydrocarbyl or aryl or optionally substituted aryl; r2Independently a linear or branched C1 to C4 alkyl group; r3Is hydrogen or C1 to C4 alkyl; r4Is a hydrocarbyl group (e.g., polyisobutylene and the like as discussed more below); r5Is hydrogen, alkyl, aryl, -OH, -NHR6A polyamine or an alkyl group containing or more primary, secondary or tertiary amino groups, and wherein R6Is hydrogen or alkyl.
In other methods or embodiments, the method of paragraph may further include one or more other features selected from any combination of wherein the ratio of the additive of formula I to the additive of formula II is from about 1:8 to about 8:1, and/or wherein the fuel composition includes from about 1.5 to about 100ppmw of the additive of formula I and from about 3 to about 800ppmw of the additive of formula II, and/or wherein the fuel composition includes no more than about 600ppmw of the fuel injector cleaning mixture, and/or wherein the fuel composition further includes from about 45 to about 1000ppmw of a separate Intake Valve Deposit (IVD) control additive selected from the group consisting of Mannich detergents, polyetheramine detergents, hydrocarbyl amine detergents, and combinations thereof, and/or wherein the fuel composition further includes at least additives selected from the group consisting of antioxidants, carrier fluids, metal deactivators, dyes, markers, corrosion inhibitors, biocides, antistatic agents, and combinations thereofAdditives, drag reducers, demulsifiers, emulsifiers, dehazers, anti-icing additives, anti-knock additives, anti-valve seat recession additives, lubricity additives, surfactants, and combustion improvers, and/or wherein the fuel injector cleaning mixture achieves about 30% to about 100% cleaning of fuel injector deposits in a gasoline engine when supplied at a pressure of about 500psi to about 7,500psi (e.g., non-idle pressure) and when cleaning of the injector deposits is measured by at least of long term fuel adjustment, injector pulse width, injection duration, injector flow rate, and combinations thereof, and/or wherein R and R' are independently alkylene linking groups having 1 to 3 carbon atoms, and R is an alkylene linking group having 1 to 3 carbon atoms1Is a C8 to C20 hydrocarbyl group; and/or wherein R' is a methylene linking group; and/or wherein R2Is methyl; and/or wherein the formula II additive comprises a hydrocarbyl-substituted succinimide derived from ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N' - (iminobis-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof; and/or wherein R in the compound of formula II4Is a hydrocarbyl group having a number average molecular weight of from about 450 to about 3000 as measured by GPC using polystyrene as a reference, and R is5Derived from tetraethylenepentamine and derivatives thereof; and/or wherein the fuel composition is provided at a pressure of from about 1,000 to about 4,000 psi; and/or wherein R1Is oleyl-derived, and wherein R5Derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-N' - (iminodi-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof; and/or wherein R and R' are independently an alkylene linking group having 1 to 3 carbon atoms, R1Is a C8 to C20 hydrocarbon group, and wherein R in the compound of formula II4Is a hydrocarbyl group having a number average molecular weight of about 450 to about 3000 as measured by GCP using polystyrene as a reference, and R is5Derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-N' - (iminobis-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof; and/or wherein R' comprises a methylene linking group; and/or wherein R2Is methyl.
Drawings
FIG. 1 is a graph showing the cleaning effectiveness of the fuel injector cleaning mixture of the present invention when combusted in a gasoline engine operating at high fuel pressures.
Detailed Description
The low treat rate of such synergistic combination of cleaning additives reduces fuel injector deposits and/or cleans fuel injectors in gasoline engines when the engine is operated at high fuel pressures (e.g., non-idle fuel pressures) above about 500psi (about 500 to about 7,500psi in processes), and in yet other processes above about 1,000psi (about 1,000 to about 7,500psi in other processes), unexpectedly found that the combination of two cleaning additives achieves a substantially higher degree of effectiveness at and a lower degree of fouling of the cleaning injectors ( in processes) than any cleaning additive alone when used in gasoline fuels at such high fuel pressures.
detergent additive:in methods, the th detergent additive of the synergistic mixture is a quaternary ammonium inner salt obtained from an amine or polyamine that is substantially free of any free anionic species
Wherein R is9、R10And R11Each being selected from hydrocarbyl groups having 1 to 200 carbon atoms, with halogen-substituted C2-C8 carboxylic acids, esters, amides or salts thereof, what is generally avoided in the reaction is a quaternizing agent selected from hydrocarbyl-substituted carboxylates, carbonates, cyclic carbonates, phenolates, epoxides or mixtures thereof, in embodiments, the halogen-substituted C2-C8 carboxylic acids, esters, amides or salts thereof may be selected from chloro-, bromo-, fluoro-and iodo-C2-C8 carboxylic acids, esters, amides and salts thereofAnd is an alkali metal or alkaline earth metal salt selected from sodium, potassium, lithium, calcium and magnesium salts. Particularly useful halogen-substituted compounds for the reaction are the sodium or potassium salts of chloroacetic acid.
As used herein, the term "substantially free of free anionic species" means that the anion is largely covalently bound to the product such that the reaction product produced does not contain any substantial amount of free anion or anion bound to the product ion in examples, "substantially free" means 0 to less than about 2 weight percent of free anionic species.
In another methods or embodiments, tertiary amines including mono-and polyamines can be reacted with halogen-substituted acetic acids or derivatives thereof to provide detergent additives of synergistic mixtures
Wherein R is9、R10And R11Each of (A) is selected from hydrocarbyl groups containing 1 to 200 carbon atoms as indicated above9To R11 representative examples of amine reactants that can be reacted to produce the compounds of the present disclosure include, but are not limited to, trimethylamine, triethylamine, tri-N-propylamine, dimethylethylamine, dimethyllaurylamine, dimethyloleylamine, dimethylstearamide, dimethyleicosylamine, dimethyloctadecylamine, N-methylpiperidine, N' -dimethylpiperazine, N-methyl-N-ethylpiperazine, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, pyridine, triethanolamine, triisopropanolamine, methyldiethanolamine, dimethylethanolamine, lauryl alcoholDiisopropanolamine, stearoyldiethanolamine, dioleylethanolamine, dimethylisobutanolamine, methyldisisooctanolamine, dimethylpropylamine, dimethylbutenylamine, dimethyloctylamine, ethyldocosahexenylamine, dibutyieicosenylamine, triethylenediamine, hexamethylenetetramine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetramethyl-propylenediamine, N, N, N ', N' -tetraethyl-1, 3-propylenediamine, methyldicyclohexylamine, 2, 6-dimethylpyridine, dimethylcyclohexylamine, amidopropyldimethylamine substituted with a C10-C30 alkyl or alkenyl group, succinic acid-carbonyl-dimethylamine substituted with a C12-C200 alkyl or alkenyl group, and the like.
If the amine contains only primary or secondary amino groups, it may be desirable to alkylate at least of the primary or secondary amino groups to tertiary amino groups prior to reaction with the halogen-substituted C2-C8 carboxylic acid, ester, amide, or salt thereof in embodiments, alkylation of the primary and secondary amines or mixture with the tertiary amine may be fully or partially alkylated to a tertiary amine.
The halogen-substituted C2-C8 carboxylic acids, esters, amides or salts thereof used to make the th cleaning additive may be derived from mono-, di-or trichloro-bromo-, fluoro-or iodo-carboxylic acids, esters, amides or salts thereof selected from the group consisting of halogen-substituted acetic acid, propionic acid, butyric acid, isopropionic acid, isobutyric acid, tert-butyric acid, valeric acid, heptanoic acid, octanoic acid, halomethylbenzoic acid and isomers, esters, amides and salts thereof.
Internal salts prepared according to the foregoing procedure can include, but are not limited to, (1) the formula R' -NMe2CH2A hydrocarbyl-substituted compound of COO, wherein R' is C1 to C30 or a substituted amido group; (2) inner salts substituted with fatty amides; and (3) an imide, amide or ester inner salt substituted with a hydrocarbon group having 8 to 40 carbon atoms. Particularly suitable internal salts may be selected from the group consisting of: polyisobutylene-substituted succinimides, succinic acid diamides, and succinic acid diester inner salts; succinimide, succinic acid diamide and succinic acid diester inner salt substituted by C8-C40 alkenyl; oleoylamidopropyl dimethylamino inner salt; and oleyl dimethylamino inner salt.
In yet another method or embodiment, the th fuel injector detergent additive of the synergistic mixture may be a quaternary ammonium inner salt of formula I
Wherein R and R' are independently an alkylene linking group having from 1 to 10 carbon atoms (and from 1 to 3 carbon atoms in other methods); r1Independently is a hydrocarbyl or optionally substituted hydrocarbyl or aryl or optionally substituted aryl; r2Independently a linear or branched C1 to C4 alkyl group; r3Is a hydrogen atom or a C1 to C4 alkyl group. As discussed above, the inner salt of formula I may also be substantially free of free anionic species.
In another methods, the fuel injector detergent additive includes a compound of formula I as described above, wherein R is a propylene linking group, R' is a methylene linking group, and R is a propylene linking group1Is a C8 to C20 hydrocarbyl group, and R2The th fuel injector detergent additive is selected from the group consisting of oleoylamidopropyl dimethylamine inner salt and oleyl dimethylamino inner salt in yet other methods, in such fuel injector detergent additives may be substantially free of free anionic species.
While the th fuel injector cleaning additive may provide limited reduction of fuel injector deposits and/or cleaning effectiveness of injector deposits in engines operating on themselves at high pressures, as discussed more below, it was unexpectedly found that when the th fuel injector cleaning additive is combined with other fuel injector cleaning additives, significantly improved cleaning effectiveness of engines is achieved when those engines are operating at high pressures.
A second detergent additive:in the processes, the second detergent additive of the synergistic mixture is a hydrocarbyl-substituted dicarboxylic anhydride derivative in the processes, the second detergent additive includes hydrocarbyl succinimides, succinamides, succinimide-amides, and succinimide-esters the nitrogen-containing derivatives of these hydrocarbyl succinic acylating agents can be prepared by reacting a hydrocarbyl-substituted succinic acylating agent with an amine, polyamine, or alkylamine having or more primary, secondary, or tertiary amino groups.
In methods or embodiments, the hydrocarbyl-substituted dicarboxylic anhydride derivatives can include hydrocarbyl substituents having a number average molecular weight in the range of about 450 to about 3000 as measured by GPC using polystyrene as a reference2N—((CHR12—(CH2)q—NH)r-H, wherein R12Is hydrogen or an alkyl group having 1 to 4 carbon atoms, q is an integer from 1 to 4, and r is an integer from 1 to 6, and mixtures thereof. The molar ratio of the hydrocarbyl-substituted dicarboxylic anhydride reacted with the ammonia, polyamine, or alkylamine can be from about 0.5:1 to about 2:1 in other processes, and from about 1:1 to about 2:1 in other processes.
In other methods, the hydrocarbyl-substituted dicarboxylic anhydride may be a hydrocarbyl carbonyl compound of formula V
Wherein R is13Is a hydrocarbyl radical derived from a polyolefin in aspects , the hydrocarbyl carbonyl compound can be a polyalkylene succinic anhydride reactant, where R is13Is a hydrocarbyl moiety, for example a polyalkenyl group having a number average molecular weight of from about 450 to about 3000 as measured by GPC using polystyrene as a reference. For example, R as measured by GPC using polystyrene as a reference13May range from about 600 to about 2500 or from about 700 to about 1500. R is particularly suitable13Has a number average molecular weight of about 950 to about 1000 daltons (as measured by GPC using polystyrene as a reference) and comprises polyisobutylene. Unless otherwise indicated, molecular weight in this specification is the number average molecular weight as measured by GPC using polystyrene as a reference.
R13The hydrocarbyl moiety may comprise or more polymer units selected from linear or branched alkenyl units in some aspects the alkenyl units may have from about 2 to about 10 carbon atoms for example the polyalkenyl group may comprise or more linear or branched polymer units selected from ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl and decenyl in some aspects R13The polyalkenyl group can be, for example, in the form of a homopolymer, copolymer, or terpolymer in the polyalkenyl group is isobutylene for example, the polyalkenyl group can be a polyisobutylene homopolymer containing from about 10 to about 60 isobutylene groups, such as from about 20 to about 30 isobutylene groups13Polyalkenyl compounds may be formed by any suitable method, for example by conventional catalytic oligomerization of olefins.
In aspects, highly reactive polyisobutenes having a relatively high ratio of polymer molecules to terminal vinylidene groups can be used to form R13In examples, at least about 60%, e.g., about 70% to about 90%, of the polyisobutylene contains terminal olefinic double bondsSex polyisobutylenes are disclosed, for example, in US 4,152,499, the disclosure of which is incorporated herein by reference in its entirety.
In some aspects of , about moles of maleic anhydride may be reacted per mole of polyalkylene such that the resulting polyalkenyl succinic anhydride has about 0.8 to about 1 succinic anhydride group per polyalkylene substituent in other aspects, the molar ratio of succinic anhydride groups to polyalkylene may be in the range of about 0.5 to about 3.5, such as about 1 to about 1.1.
examples of methods of forming hydrocarbyl carbonyl compounds include blending polyolefin and maleic anhydride heating the polyolefin and maleic anhydride reactants to a temperature of, for example, about 150 ℃ to about 250 ℃, optionally with the use of a catalyst such as chlorine or peroxide Another exemplary method of preparing polyalkylene succinic anhydride is described in U.S. Pat. No. 4,234,435, which is incorporated herein by reference in its entirety.
In the polyamine is an ethylene polyamine which may be selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and N, N' - (iminobis-2, 1, ethanediyl) bis-1, 3-propanediamine A particularly useful ethylene polyamine is of the formula H2N—((CHR12—(CH2)q—NH)rA compound of formula-H, wherein R12Is hydrogen, q is 1, and r is 4.
In yet other methods, the second fuel injector detergent additive of the synergistic mixture is a compound of formula II
Wherein R is4Is a hydrocarbon radical (e.g. polyisobutene and/or other radicals R mentioned above)13Moiety), and R5Is hydrogen, alkyl, aryl, -OH, -NHR6Or polyaminesOr alkyl containing or more primary, secondary or tertiary amino groups in methods 5Derived from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N' - (iminodi-2, 1, ethanediyl) bis-1, 3-propanediamine, and combinations thereof. In yet other methods, R5Is a compound of formula VI
Wherein A is NR6Or an oxygen atom, R6、R7And R8Independently a hydrogen atom or an alkyl group, m and p are integers from 2 to 8, and n is an integer from 0 to 4 in methods R of formula VI7And R8Together with the nitrogen atom to which it is attached, form a 5-membered ring.
Synergistic cleaning mixture:the fuel-soluble synergistic cleaning mixture of the cleaning additive and the second cleaning additive described above is effective to reduce deposits on fuel injectors, and in particular to clean fuel injectors that have fouled in gasoline engines operating at fuel pressures, e.g., non-idle fuel pressures, greater than 500psi, and in other methods, from about 500 to about 7,500psi (in yet other methods, greater than about 1,000psi and/or from about 1,000psi to about 7,500 psi.) by cleaning, it is meant to reduce or eliminate existing fuel injector deposits in gasoline engines when operated at such high pressuresThis further steps in methods enable the addition of other additives to the fuel.
In other methods or embodiments, the fuel soluble synergistic detergent mixture as described in the preceding paragraph is added to the gasoline fuel in an amount of up to about 1,000ppmw (in other methods up to about 600ppmw, in still other methods up to about 400ppmw, up to about 100ppmw, up to about 50ppmw, up to about 15ppmw, and/or up to about 12ppmw) of the fuel soluble synergistic detergent mixture having a ratio of the detergent additive to the second detergent additive of from about 1:8 to about 8: 1.
In other processes, the fuel composition comprises from about 1.5 to about 100ppmw (in other processes from about 1.5 to about 60ppmw, in still other processes from about 1.5 to about 20ppmw, from about 15 to about 10ppmw, from about 1.5 to about 5ppmw) of the clean additive described herein and from about 3 to about 800ppmw (in other processes from about 3 to about 400ppmw, in other processes from about 3 to 100ppmw, from about 3 to about 50ppmw, from about 3 to about 20ppmw, and/or from about 3 to about 1ppmw or from about 7 to about 20ppmw) of the second clean additive described herein, wherein the ratio of the clean additive to the second clean additive is maintained from about 1:8 to about 8:1, and in other processes from about 1:2 to about 2:1, and in still other processes from about 1: 2.
The fuel soluble synergistic cleaning mixture herein (as described in all preceding paragraphs) surprisingly achieves cleaning of about 30 to about 100% from fuel injector deposits when cleaning is measured by long term fuel adjustment (LTFT), injector pulse width, injection duration and/or injector flow to suggest only a few methods of measuring injector cleanliness when combusting gasoline fuel with a fuel soluble synergistic cleaning mixture in an engine operating at a fuel pressure of about 500 to about 7,500psi in methods, as discussed further below at , fuel injector deposit cleaning is measured according to SAE 2013-01-2626 and/or SAE2017-01-2298, both of which are incorporated herein by reference in their entirety.
Hydrocarbon fuel:the base fuels used to formulate the fuel compositions of the present disclosure include any base fuel suitable for operation in gasoline engines configured to combust fuels at the high fuel pressures discussed herein. Suitable fuels include leaded or unleaded motor gasoline and so-called reformulated gasoline, which typically contains hydrocarbons in the gasoline boiling range and fuel-soluble oxygenated blending agents ("oxygenates"), such as alcohols, ethers and other suitable oxygenated organic compounds. Preferably, the fuel is a mixture of hydrocarbons boiling in the gasoline boiling range. Such fuels may be comprised of straight or branched chain paraffins, cycloparaffins, olefins, aromatic hydrocarbons, or any mixture of these. The gasoline may be derived from straight run naphtha, polymer gasoline, natural gasoline, or catalytically reformed feedstocks boiling in the range of about 80F to about 450F. The octane content of the gasoline is not critical and any conventional gasoline may be used in the practice of the present invention.
Oxygenates suitable for use in the present invention include methanol, ethanol, isopropanol, t-butanol, mixed C1 to C5 alcohols, methyl t-butyl ether, t-amyl methyl ether, ethyl t-butyl ether, and mixed ethers. When used, oxygenates are typically present in the base fuel in an amount less than about 30 volume percent, and preferably in an amount to provide an oxygen content in the total fuel in the range of about 0.5 to about 5 volume percent.
High pressure gasoline engines are known to those of ordinary skill in the art and are configured to operate on non-idle gasoline fuel above about 500psi or above 1,000psi, and preferably from about 500 to about 7,500psi (about 1,000 to about 7,500psi, about 500 to about 4,000psi, about 1,000 to about 4,000psi, and in yet other methods about 500 to about 3,000psi or about 1,000 to about 3,000psi), hydrocarbon fuel boiling in the gasoline range may spark or compression ignite at such high pressures.
Supplemental fuel additive: in addition to the fuel-soluble synergistic detergent mixtures described above, the fuel compositions of the present disclosure may also contain supplemental additives. For example, supplemental additives may include other dispersants/detergents, antioxidants, carrier fluids, metal deactivators, dyes, markers, corrosion inhibitors, biocides, antistatic additives, drag reducing agents, demulsifiers, emulsifiers, dehazers, anti-icing additives, anti-knock additives, anti-valve seat recession additives, lubricity additives, surfactants, combustion improvers, and mixtures thereof.
Mannich base detergents suitable for use in the fuel compositions herein include the reaction product of a hydroxy aromatic compound substituted with a high molecular weight alkyl group, an aldehyde, and an amine, if used, the fuel composition may include from about 45 to about 1000ppm of the Mannich base detergent as the sole IVD control additive.
In methods, the high molecular weight alkyl substituent on the benzene ring of the hydroxyaromatic compound can be derived from a polyolefin having a number average molecular weight (Mn) of from about 500 to about 3000, preferably from about 700 to about 2100, as determined by Gel Permeation Chromatography (GPC) using polystyrene as a reference the polydispersity (weight average molecular weight/number average molecular weight) of the polyolefin can also be from about 1 to about 4 (otherwise from about 1 to about 2), as determined by GPC using polystyrene as a reference.
The alkylation of hydroxyaromatic compounds is generally carried out in the presence of an alkylation catalyst at a temperature in the range of from about 0 to about 200 c, preferably 0 to 100 c. Acidic catalysts are commonly used to promote Friedel-Crafts alkylation. Typical catalysts for commercial production include sulfuric acid, BF3Aluminum phenolate, methanesulfonic acid, cation exchange resin, acidic clay, and modified zeolite.
Polyolefins suitable for use in forming hydroxyaromatic compounds substituted with high molecular weight alkyl groups include polypropylene, polybutene, polyisobutylene, copolymers of butene and/or butene and propylene, copolymers of butene and/or isobutylene and/or propylene, and one or more monoolefin comonomers copolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), wherein the copolymer molecules contain at least 50 weight percent butene and/or isobutylene and/or propylene units.
Unless otherwise specified herein, the term "polybutene" is used in the sense of to include polymers made from "pure" or "substantially pure" 1-butene or isobutylene, as well as polymers made from mixtures of two or all three of 1-butene, 2-butene and isobutylene commercial grades of such polymers may also contain insignificant amounts of other olefinsThe vinyl isomer. Suitable polyisobutenes include the use of BF3Catalyst prepared polyisobutene. The preparation of such polyisobutenes, in which the methylvinylidene isomer constitutes a high percentage of the total composition, is described in US 4,152,499 and US 4,605,808, both of which are incorporated herein by reference.
Mannich detergents can be made from high molecular weight alkylphenols or alkyl cresols. However, other phenolic compounds may be used, including high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, and the like. Preferred for use in preparing the Mannich detergents are polyalkylphenol and polyalkylcresol reactants, such as polypropylphenol, polybutylphenol, polypropylcresol, and polybutylcresol, wherein the alkyl group has a number average molecular weight of from about 500 to about 2100 as measured by GPC using polystyrene as a reference, and most preferably the alkyl group is a polybutyl group derived from polyisobutylene having a number average molecular weight in the range of from about 700 to about 1300 as measured by GPC using polystyrene as a reference.
However, any hydroxyaromatic compound that readily reacts in the Mannich condensation reaction may be employed, therefore, Mannich products made from hydroxyaromatic compounds having only cycloalkyl substituents or two or more cycloalkyl substituents are suitable for use in the present invention.
Representative amine reactants include, but are not limited to, alkylene polyamines having at least suitably reactive primary or secondary amino groups in the molecule other substituents such as hydroxyl, cyano, amido, and the like can be present in the polyamine in the preferred embodiment the alkylene polyamine is a polyethylene polyamine suitable alkylene polyamine reactants include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and mixtures of such amines having a nitrogen content corresponding to the formula H2N--(A-NH--)nH, wherein A in formula is a divalent ethylene or propylene group, and n is an integer of 1 to 10, preferably 1 to 4. the alkylene polyamine can be obtained by reacting ammonia with a dihaloalkane, such as dichloroalkane.
Examples of suitable polyamines include N, N "-tetraalkyldialkylenetriamines (two terminal tertiary amino groups and central secondary amino groups), N ', N" -tetraalkyltrialkylenetetramines ( terminal tertiary amino groups, two internal tertiary amino groups and terminal primary amino groups), N ', N "-tetraalkyltrialkylenetetramines ( terminal tertiary amino groups, two internal tertiary amino groups and terminal secondary amino groups), N-dihydroxyalkyl- -, ω -alkylenediamine ( terminal tertiary amino groups and terminal primary amino groups), N ' -trihydroxyalkyl- , ω -alkylenediamine ( terminal tertiary amino groups and terminal secondary amino groups), tris (dialkylaminoalkyl) aminoalkylmethanes (three terminal tertiary amino groups and terminal primary amino groups) and similar compounds, wherein the alkyl groups are the same or different and each contain from about 1 to about 12 carbon atoms, and most preferably the reactants are from about 1 to about 3 alkyl-methyl-containing from about 1 to about 12 carbon atoms, and most preferably from about 3 alkyl-alkylene-piperazine, each of these reactants is from about 1 to about 12 carbon atoms, and most preferably from about 3 alkyl-alkylene-1 to about 3 methyl-alkylene-piperazine.
Examples of polyamines having reactive primary or secondary amino groups which can participate in the Mannich condensation reaction and at least sterically hindered amino groups which cannot directly participate in the Mannich condensation reaction to any significant extent include N- (tert-butyl) -1, 3-propanediamine, N-neopentyl-1, 3-propanediamine, N- (tert-butyl) -1-methyl-1, 2-ethanediamine, N- (tert-butyl) -1-methyl-1, 3-propanediamine and 3, 5-di (tert-butyl) aminoethylpiperazine.
Representative aldehydes for use in the preparation of the Mannich base products include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde. Aromatic aldehydes which may be used include benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes for use in the present invention are furfural and thiopheneal aldehyde, and the like. Also useful are formaldehyde-generating agents, such as paraformaldehyde or aqueous formaldehyde solutions, such as formalin. Most preferred is formaldehyde or formalin.
The condensation reaction between the alkylphenol, the specific amine, and the aldehyde can be carried out at a temperature generally in the range of about 40 ℃ to about 200 ℃. The reaction may be carried out in bulk (without diluent or solvent) or in a solvent or diluent. Water escapes and can be removed by azeotropic distillation during the reaction. Generally, the Mannich reaction product is formed by reacting an alkyl-substituted hydroxyaromatic compound, an amine, and an aldehyde in a molar ratio of 1.0:0.5 to 2.0:1.0 to 3.0, respectively.
Suitable mannich base detergents include US 4,231,759; US 5,514,190; US 5,634,951; US 5,697,988; US 5,725,612; and those taught in 5,876,468, the disclosures of which are incorporated herein by reference.
Another suitable additional fuel additive may be a hydrocarbyl amine detergent if used, the fuel composition may include from about 45 to about 1000ppm of a hydrocarbyl amine detergent a common process involves the conversion of at least some products to amine salts by treatment with an appropriate amount of acid if desired, the products formed by the halogenation route typically containing a small amount of residual halogen, e.g., chlorine, another means to produce a suitable aliphatic polyamine involves controlled oxidation (e.g., with air or peroxide) of a polyolefin, e.g., polyisobutylene, followed by reaction of the oxidized polyolefin with a polyamine, see, e.g., U.S. Pat. No. ; No. ; see, e.g., U.S. Pat. ; , .
Polyetheramines are yet another suitable additional detergent chemicals for the process of this disclosure the fuel composition, if used, may include from about 45 to about 1000ppm of polyetheramine detergents the polyether backbone in such detergents may be based on propylene oxide, ethylene oxide, butylene oxide or mixtures thereof, most preferably propylene oxide or butylene oxide or mixtures thereof to impart good fuel solubility the polyetheramines may be monoamines, diamines or triamines examples of commercially available polyetheramines are those available under the trade name jeffamines (tm) from Huntsman Chemical Company and poly (oxyalkylene) urethanes available from chevron Chemical Company (chevron Chemical Company) the molecular weight of polyetheramines will generally range from 500 to 3000 other suitable polyetheramines are those taught in U.S. patent nos. 4,191,537, No. 4,236,020, No. 4,288,612, No. 5,089,029, No. 5,112,364, No. 5,322,529, No. 5,56,514 and No. 5,522,906.
In the methods of , the fuel-soluble synergistic detergent mixture can also be used with a liquid carrier or inducement aid . these carriers can be of various types, such as liquid poly- α -olefin oligomers, mineral oils, liquid poly (oxyalkylene) compounds, liquid alcohols or polyols, polyolefins, liquid esters, and similar liquid carriers.
Exemplary liquid vehicles may include mineral oils or blends of mineral oils having a viscosity index of less than about 120, or more poly- α -olefin oligomers, or more poly (oxyalkylene) compounds having an average molecular weight in the range of about 500 to about 3000, polyolefins, hydroxyaromatic compounds substituted with polyalkyl groups, or mixtures thereof.
Poly- α -olefins (PAOs) suitable for use as carrier fluids are hydrotreated and unhydrogenated poly- α -olefin oligomers, such as hydrogenated or unhydrogenated products, primarily trimers, tetramers and pentamers of α -olefin monomers, wherein the monomers contain 6 to 12, typically 8 to 12, most preferably about 10 carbon atoms, the synthesis of which is outlined in section "Hydrocarbon Processing", 2.1982, p.75 and below and in U.S. Pat. No. 3,763,244; No. 3,780,128; 4,172,855; No. 4,218,330; and No. 4,950,822. common processes primarily comprise the catalytic oligomerization of short chain linear α -olefins (suitably obtained by catalytic treatment of ethylene.) the viscosity of poly- α -olefins used as carriers (measured at 100 ℃) will typically be in the range of 2 to 20 centistokes (cSt.) preferably, the viscosity of poly- α -olefins at 100 ℃ is at least 8cSt, and most preferably about 10 cSt.
Suitable poly (oxyalkylene) compounds for the carrier liquid can be fuel-soluble compounds, which can be represented by the formula
RA--(RB-O)w--RC
Wherein R isATypically hydrogen, alkoxy, cycloalkoxy, hydroxy, amino, hydrocarbyl (e.g., alkyl, cycloalkyl, aryl, alkaryl, aralkyl, etc.), hydrocarbyl substituted with an amino group, or hydrocarbyl substituted with a hydroxy group, RBIs an alkylene group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, RCTypically hydrogen, alkoxy, cycloalkoxy, hydroxy, amino, hydrocarbyl (e.g., alkyl, cycloalkyl, aryl, alkaryl, aralkyl, etc.), hydrocarbyl substituted with an amino, or hydrocarbyl substituted with a hydroxy group, and w is an integer from 1 to 500, and preferably in the range of from 3 to 120, which represents the number (typically the average number) of repeating alkyleneoxy groups. In a structure having a plurality of- -RBIn compounds of the group- -O- - - - -, RBThe preferred poly (oxyalkylene) compounds are monoalcohols comprising repeat units formed by reacting an alcohol with or more alkylene oxides, preferably alkylene oxides, more preferably propylene oxide or butylene oxide.
The poly (oxyalkylene) compounds used as carrier fluids preferably have an average molecular weight in the range of from about 500 to about 3000, more preferably from about 750 to about 2500, and most preferably from above about 1000 to about 2000.
A subgroup of useful poly (oxyalkylene) compounds comprises hydrocarbyl-terminated poly (oxyalkylene) monools, such as those mentioned in the paragraphs from column 6, line 20 to column 7, line 14 of U.S. patent No. 4,877,416, and references listed in said paragraphs, which paragraphs and references are incorporated herein by reference in their entirety.
Another subgroup of poly (oxyalkylene) compounds includes or mixtures of alkyl poly (oxyalkylene) monools which in their undiluted state are gasoline soluble liquids having a viscosity of at least about 70 centistokes (cSt) at 40℃ and at least about 13cSt at 100℃.
The viscosity of the poly (oxyalkylene) carrier in its undiluted state can be at least about 60cSt at 40 ℃ (in other methods, at least about 70cSt at 40 ℃) and at least about 11cSt at 100 ℃ (more preferably at least about 13cSt at 100 ℃). Further, the poly (oxyalkylene) compounds used in the practice of the present invention preferably have a viscosity in their undiluted state of no more than about 400cSt at 40 ℃ and no more than about 50cSt at 100 ℃. In other processes, the viscosity is typically no more than about 300cSt at 40 ℃ and typically no more than about 40cSt at 100 ℃.
Preferred poly (oxyalkylene) compounds also include poly (oxyalkylene) glycol compounds and monoether derivatives thereof which meet the above viscosity requirements and comprise repeating units formed by reacting an alcohol or polyol with an alkylene oxide (e.g., propylene oxide and/or butylene oxide) with or without the use of ethylene oxide, and especially products wherein at least 80 mole percent of the oxyalkylene groups in the molecule are derived from 1, 2-propylene oxide. Details concerning the preparation of such poly (oxyalkylene) compounds are mentioned, for example, in "Kirk-Othmer, Encyclopedia of chemical Technology", 3 rd edition, volume 18, page 633-once 645 (1982 copyright of John Wiley & Sons) and references cited therein, the aforementioned excerpts of the "cockamamer Encyclopedia" and references cited therein being incorporated herein by reference. U.S. patent No. 2,425,755; 2,425,845 No; 2,448,664 No; and 2,457,139, are also described and are incorporated by reference herein in their entirety.
When a poly (oxyalkylene) compound is used, it typically contains a sufficient number of branched oxyalkylene units (e.g., methyldimethyleneoxy units and/or ethyldimethyleneoxy units) to render the poly (oxyalkylene) compound gasoline soluble. Suitable poly (oxyalkylene) compounds include those described in U.S. Pat. nos. 5,514,190; nos. 5,634,951; nos. 5,697,988; nos. 5,725,612; 5,814,111 and 5,873,917, the disclosures of which are incorporated herein by reference.
Polyolefins suitable for use as carrier fluids include polypropylene and polybutylene, the polyolefins may have a polydispersity (Mw/Mn) of less than 4. in examples, the polyolefins have a polydispersity of 1.4 or less. typically, the polybutenes have a number average molecular weight (Mn) of from about 500 to about 2000, preferably from 600 to about 1000, as determined by Gel Permeation Chromatography (GPC). polyolefins suitable for use in the present invention are taught in U.S. Pat. No. 6,048,373.
Suitable polyalkyl-substituted hydroxyaromatic compounds useful as carrier fluids include those known in the art, such as those described in U.S. Pat. Nos. 3,849,085; nos. 4,231,759; 4,238,628 No; 5,300,701 No; 5,755,835 and 5,873,917, the disclosures of which are incorporated herein by reference.
Definition of
For purposes of this disclosure, chemical elements are identified in accordance with the Periodic Table of the elements, CAS edition, Handbook of Chemistry and Physics, 75 th edition. In addition, general principles of Organic Chemistry are described in "Organic Chemistry" (Organic Chemistry), "Thomas Sorrell," University Science Books, "Sausolato: 1999 and" March's Advanced Organic Chemistry "(5 th edition, Smith, M.B., and March, J. eds., John Williams' Corp., New York (New York):2001, the entire contents of which are incorporated herein by reference.
As used herein, the term "substantial amount" is understood to mean an amount greater than or equal to 50% by weight, such as from about 80 to about 98% by weight, relative to the total weight of the composition. Furthermore, as used herein, the term "minor amount" is understood to mean an amount of less than 50% by weight relative to the total weight of the composition.
As described herein, the compounds may be optionally substituted with or more substituents, such as illustrated above by , or as exemplified by particular classes, subclasses, and species of the disclosure.
As used herein, "alkyl" refers to a saturated aliphatic hydrocarbon group containing (unless otherwise indicated in this disclosure) 1 to 12 (e.g., 1 to 8,1 to 6, or 1 to 4) carbon atoms]Heterocycloaliphatic [ e.g. heterocycloalkyl or heterocycloalkenyl ]]Aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [ e.g. (aliphatic) carbonyl, (cycloaliphatic) carbonyl or (heterocycloaliphatic) carbonyl]Nitro, cyano, acylamino [ e.g. (cycloalkylalkyl) carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl) carbonylamino, (heterocycloalkylalkyl) carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl]Amino group [ e.g. aliphatic amino group, cycloaliphatic amino group or heterocycloaliphatic amino group]Sulfonyl [ e.g. aliphatic-SO2-]Sulfinyl, thio, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, pendant oxy, carboxyl, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkoxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxyl non-limiting examples of substituted alkyl groups include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl) alkyl, (sulfonylamino) alkyl (e.g., (alkyl-SO)2-amino) alkyl), aminoalkyl, amidoalkyl, (cycloaliphatic) alkyl or haloalkyl.
As used herein, "alkenyl" is meant to contain (unless otherwise indicated herein, otherwise specifically stated)Disclosed are) aliphatic carbon groups of 2-8 (e.g., 2-12, 2-6, or 2-4) carbon atoms and at least double bonds, and alkyl -like, alkenyl can be straight or branched]Heterocycloaliphatic [ e.g. heterocycloalkyl or heterocycloalkenyl ]]Aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [ e.g. (aliphatic) carbonyl, (cycloaliphatic) carbonyl or (heterocycloaliphatic) carbonyl]Nitro, cyano, acylamino [ e.g. (cycloalkylalkyl) carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl) carbonylamino, (heterocycloalkylalkyl) carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl or heteroarylaminocarbonyl]Amino group [ e.g., aliphatic amino group, cycloaliphatic amino group, heterocyclic aliphatic amino group or aliphatic sulfonylamino group]Sulfonyl [ e.g. alkyl-SO)2-, cycloaliphatic-SO2-or aryl-SO2-]Sulfinyl, thio, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, pendant oxy, carboxyl, carbamoyl, cycloaliphatic oxy, heterocycloaliphatic oxy, aryloxy, heteroaryloxy, aralkoxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxyl non-limiting examples of substituted alkenyl include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl) alkenyl, (sulfonylamino) alkenyl (e.g., (alkyl-SO)2-amino) alkenyl), aminoalkenyl, amidoalkenyl, (cycloaliphatic) alkenyl, or haloalkenyl.
"hydrocarbyl" refers to a group having carbon atoms directly attached to the remainder of the molecule and each hydrocarbyl is independently selected from hydrocarbon substituents and substituted hydrocarbon substituents that may contain or more of halo, hydroxy, alkoxy, mercapto, nitro, nitroso, amino, sulfoxy, pyridyl, furanyl, thienyl, imidazolyl, sulfur, oxygen, and nitrogen, and wherein no more than two non-hydrocarbon substituents are present per ten carbon atoms in the hydrocarbyl group.
As used herein, fuel-soluble generally means that the material should be sufficiently soluble (or dissolved) in the base fuel at about 20 ℃ at least at the minimum concentration required for the material to perform its intended function. Preferably, the substance will have significantly greater solubility in the base fuel. However, the substance need not be dissolved in the base fuel in all proportions.
The number average molecular weight (Mn) of any of the methods, aspects, embodiments, or examples herein can be determined with Gel Permeation Chromatography (GPC) equipment obtained from Waters or the like, and the data processed, e.g., with Waters Empower software or the like. The GPC instrument may be equipped with a volterra separation module and a volterra refractive index detector (or similar optional equipment). GPC operating conditions may include guard columns, 4 Agilent PLGel columns (300X 7.5mm in length; 5 μ in particle size, and pore size
A better understanding of the present disclosure and many of its advantages may be set forth in the following examples. The following examples are illustrative and do not limit the scope or spirit thereof. Those of skill in the art will readily appreciate that variations of the components, methods, steps, and apparatuses described in these examples may be used. All percentages, ratios, and parts mentioned in this disclosure are by weight unless otherwise indicated or apparent from the context of the discussion.
Examples of the invention
Example 1
FIG. 1 illustrates the percent cleanliness of gasoline engines fuelled with three different fuel injector cleaning additives between about 580 and about 1,960psi, about 3.8ppmw of oil-based dimethylaminopropyl betaine, about 7.6ppmw of PIBSA-TEPA additive, and 3.8ppmw of betaine, with a synergistic combination of the present invention of about 7.6ppmw of PIBSA-TEPA cleaning additive (1:2 ratio).
As shown in fig. 1, while the betaine detergent additive alone provides a modest degree of fuel injector cleanliness when combusted in a gasoline engine operating at fuel injection of about 580 to about 1,960psi, the PIBSA-TEPA additive does not provide cleaning efficacy in high pressure fuel at 7.6 ppmw. However, the PIBSA-TEPA combined addition with betaine (2:1 ratio) demonstrated a significant increase in fuel injector cleaning performance when operating at high gasoline fuel injection pressures. Given that the PIBSA-TEPA additive has no cleaning efficacy in high pressure gasoline engines at 7.6ppmw, the combination of PIBSA-TEPA and betaine is not expected to cause an increase in cleaning rate relative to betaine alone. This synergistic combination of the two additives delivered resulted in about twice the cleaning rate of betaine by operating the engine for 2000 miles at high fuel pressures.
High pressure Gasoline engine tests were evaluated for additive capability to clean fouled Injectors in high pressure fuel injected engines using the procedures set forth in Shanahan, C., Smith, S., and Sears, B., "the effect of common methods and deposits used to foul Injectors and deposit on Vehicle Performance in Gasoline Direct Injection Vehicles" (A General Method for fouling Injectors in Gasoline Direct Injection Vehicles) "journal of American society of automotive Engineers International Fuel and lubricating oil (SAEInt. J. fuels) 10(3):2017, doi:10.4271/2017-01-2298, which is incorporated herein by reference and discussed further below. , while the tests herein use KiaOpa engines, Kittim observations and results are applicable to other Vehicle manufacturers, engine models, and other high pressure fuel injected engines.
Testing involved the use of fuel blends to accelerate into the dirty phase of the engine or injector fouling. The accelerated E0 gasoline blend comprised 409ppmw of di-tert-butyl disulfide (DTBDS, contributing about 147ppmw of active sulfur to the fuel) and 286ppmw of tert-butyl hydroperoxide (TBHP). The test involved running a 2013Kia Optima on a mileage accumulating dynamometer with a 2.4L, 16-valve, in-line 4 gasoline high pressure direct injection engine. The engine was operated using a "Quad 4" drive cycle as set forth in the society of automotive Engineers paper (SAE paper) mentioned above (SAE2017-01-2298) and as set forth in Table 1 below. Injector cleanliness is measured as reported by a vehicle Engine Control Unit (ECU) using long term fuel adjustment (LTFT), and is measured relative to accumulated mileage. The test results are shown in fig. 1. The percent clean is the change in LTFT from the start of the test relative to the LTFT at a predetermined mile test point.
Table 1: quad 4 drive cycle
It is to be understood that while the fuel additives, compositions and methods of the present disclosure have been described in conjunction with the embodiments and summary thereof herein, the foregoing description is intended to illustrate and not limit the scope of the disclosure, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the claims. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims.
As used throughout this specification and the claims, " (a)" and/or " (an)" may refer to or more than unless otherwise indicated, all numbers expressing quantities of ingredients, properties, such as molecular weight, percentages, ratios, reaction conditions, and the like, used in this specification are to be understood as being modified in all instances by the term "about," whether or not the term "about" is present.
It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as disclosed for use alone or in combination with or more of each other components, compounds, substituents or parameters disclosed herein.
It should also be understood that each range disclosed herein should be interpreted as disclosing each particular value with the same number of significant digits within the disclosed range.thus, for example, a range of 1 to 4 should be interpreted as specifying a value of 1,2, 3, and 4 and any range for those values.it should further be understood that also discusses any range between the end points within the described ranges.
It will also be understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent or parameter. Accordingly, this disclosure is to be construed as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range.
Further, specific amounts/values of a component, compound, substituent or parameter disclosed in the specification or examples should be interpreted as a disclosure of the lower or upper limit of the range and thus may be combined with any other lower or upper limit or specific amount/value of the range of the same component, compound, substituent or parameter disclosed elsewhere in this application to form the range of the component, compound, substituent or parameter.
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